107-86-8Relevant articles and documents
Bergmann
, p. 1218 (1951)
Copper-doped sulfonic acid-functionalized MIL-101(Cr) metal–organic framework for efficient aerobic oxidation reactions
Li, Xiujuan,Zhou, Zihao,Zhao, Yuzhen,Ramella, Daniele,Luan, Yi
, (2020)
A series of Cr-based metal–organic framework MIL-101-SO3H bearing sulfonic acid functional groups were utilized for the immobilization of catalytically active copper species via a post-synthetic metalation method. The novel materials were fully characterized by scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller method, and thermogravimetric analysis. XPS and the EDX element map both suggested that Cu2+ is coordinately bonded to the MIL-101-SO3H, which forms the MIL-101-SO3@Cu structure. The obtained copper-doped MIL-101-SO3@Cu-1, MIL-101-SO3@Cu-2, and MIL-101-SO3@Cu-3 catalysts were utilized in the selective oxidation of alcohols and epoxidation of olefins using molecular oxygen as an oxidant. Catalytic aerobic oxidation optimization showed that MIL-101-SO3@Cu-1 is the optimal catalyst and it can be reused ten times without compromising the yield and selectivity.
Studies on the synthesis of elegan-type linear diterpenes: The efficient total syntheses of eleganolone, eleganolone acetate, elegandiol, eleganonal, and epoxyeleganolone
Li,Lan,Liu,Li
, p. 92 - 95 (1998)
The first total syntheses of five elegan-type linear diterpenes- eleganolone (1), eleganolone acetate (2), elegandiol (3), eleganonal (4), and epoxyeleganolone (5)-were accomplished starting from (E,E)-farnesol (6) via four to six steps, successively, with high overall yield. The key step was the alkylation reaction of silyl cyanide with allylic iodide.
A comparison of intrazeolite and solution singlet oxygen ene reactions of allylic alcohols
Clennan, Edward L.,Zhang, Dong,Singleton, Jamie
, p. 1226 - 1232 (2006)
The singlet oxygen ene reactions of four allylic alcohols and for comparison an allylic ether have been examined both in solution and in zeolite Y. Bronsted acid sites in the zeolite were shown to induce decomposition of several of the allylic alcohols. Treatment of the zeolites with pyridine removed these acid sites and allowed intrazeolite reactions of the allylic alcohols without interference from decomposition. Control reactions with an allylic alcohol that is inert to decomposition provided evidence that the presence of pyridine in the zeolite labyrinth does not influence the product composition.
A highly recyclable magnetic core-shell nanoparticle-supported TEMPO catalyst for efficient metal- and halogen-free aerobic oxidation of alcohols in water
Karimi, Babak,Farhangi, Elham
, p. 6056 - 6060 (2011)
The selective oxidation of primary and secondary alcohols to the corresponding carbonyl compounds is one of the most challenging reactions in organic chemistry. Many oxidizing reagents such as stoichiometric CrVI salts, DMSOcoupled reagents, and hypervalent iodine have been traditionally used to accomplish this transformation. However, these reagents show poor atom efficiency and are often toxic; their widespread use thereby causes significant environmental concerns that render them impractical. As a consequence, due to ever-increasing environmental standards and economic pressures, there is substantial interest towards the use of heterogeneous and recyclable catalysts to achieve the efficient oxidation of alcohols with molecular oxygen or air as the oxidant. Whereas methodologies for the improvement of catalytic activities and selectivities have been developed considerably, they may possibly leave toxic traces of heavy metals in the products. Moreover, many of the metal-based catalyst systems are often deactivated because of the occupation of coordination sites with the by-produced water and so they generally require the use of organic solvents. Therefore, it seems that there is still a great interest in developing efficient and non-metallic catalysts for the aerobic oxidation of alcohols from the viewpoint of socalled green and sustainable chemistry. Of particular interest in this area is the application of the stable nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) in combination with various types of non-metallic, stoichiometric co-oxidants as an alternative to metal-based oxidants.
Shape-selective isomerisation of α-acetylenic alcohols to α,β-ethylenic carbonyl compounds by vanadium-pillared montmorillonite catalyst
Choudary,Durga Prasad,Valli
, p. 7521 - 7522 (1990)
A very simple, convenient method for an efficient shape-selective isomerisation of acyclic and aromatic α-acetylenic alcohols only, to the corresponding α,β-ethylenic carbonyl compounds, leaving the cyclic ones unreacted using catalytic amounts of vanadium-pillared montmorillonite catalyst, having -Si-O-V=0 groups with successful reusability is described.
Au/Cu-fiber catalyst with enhanced low-temperature activity and heat transfer for the gas-phase oxidation of alcohols
Zhao, Guofeng,Hu, Huanyun,Deng, Miaomiao,Ling, Min,Lu, Yong
, p. 55 - 58 (2011)
A microfibrous-structured gold catalyst was successfully prepared by gold galvanic deposition on a thin-sheet sinter-locked Cu-fibers. The catalyst has excellent heat transfer ability and enhanced low-temperature activity suitable for gas-phase oxidation of alcohols. The AuCu(alloy)-Cu2O active composites formed during reaction and their cooperative effect contribute to promoting the low-temperature activity.
Selective organic transformation over a self-assembled all-solid-state Z-scheme core-shell photoredox system
Fu, Xiao-Yan,Hou, Shuo,Lin, Xin,Mo, Qiao-Ling,Wei, Zhi-Quan,Xiao, Fang-Xing,Xu, Shuai
, p. 20151 - 20161 (2020)
Z-Scheme artificial photosystems, resembling the natural photosynthesis procedure, circumvent the disadvantage of a single-ingredient photosystem and hold fascinating prospects for solar energy conversion. Despite the advancements, bottom-up elaborate design of composite heterostructured Z-scheme photosystems by flexible interface engineering for photoredox organic transformation has been poorly investigated. We herein report the construction of a metal-based Z-scheme photoredox systemviaa progressive self-assembly strategy integrated with a facile photo-deposition. Tailor-made hierarchically branched ligand-capped Pd nanocrystals (NCs) sandwiched in-between a WO3nanorod (NR) core and CdS shell are harnessed as the charge transport modulator to regulate the interfacial oxidation-reduction kinetics for boosted Z-scheme photocatalysis. The intermediate Pd NCs as Schottky-type electron flow mediators considerably accelerate the unidirectional Z-scheme charge motion rate, endowing multilayered WO3?Pd?CdS core-shell heterostructures with significantly boosted net efficiency of photoactivities toward anaerobic selective nitroaromatic reduction to amino derivatives and aromatic alcohol oxidation to aldehydes under visible light illumination. The predominant active species produced in the versatile photocatalytic selective organic transformation were explored and photocatalytic mechanisms were thus ascertained. Our endeavor could offer a promising route for smartly crafting diverse heterostructured Z-scheme photoredox systems for solar energy conversion.
Supported palladium nanoparticles on hybrid mesoporous silica: Structure/activity-relationship in the aerobic alcohol oxidation using supercritical carbon dioxide
Hou, Zhenshan,Theyssen, Nils,Brinkmann, Axel,Klementiev, Konstantin V.,Gruenert, Wolfgang,Buehl, Michael,Schmidt, Wolfgang,Spliethoff, Bernd,Tesche, Bernd,Weidenthaler, Claudia,Leitner, Walter
, p. 315 - 323 (2008)
The preparation, characterization, and catalytic properties of Pd nanoparticles supported on mesoporous organic-inorganic hybrid materials are described for continuous-flow aerobic oxidation of alcohols using supercritical carbon dioxide (scCO2) as a mobile phase. The nanoparticles were generated "bottom-up" from molecular precursors that were precoordinated to the support through suitable anchor units. The most active material allows high single-pass conversions in scCO2 at temperatures as low as 60 °C. This high activity may be associated with the presence of small primary crystallites (approx. 2 nm) that conglomerate to ensembles about 25 nm in size, leading to a larger number of high-indexed planes in small volume units. These findings may provide useful guidelines for further catalyst design on the nanoscale for green oxidation methods.
First total synthesis of (±) Hedaol B
Li, Ying,Lu, Biao,Li, Chunhong,Li, Yulin
, p. 1417 - 1423 (2003)
Hedaol B, a new bisnorditerpene isolated from the Japanese brown alga Sargassum. sp., was first synthesized starting from geranyl acetone, alkylation of silyl cyanide as the key step.
MagtrieveTM an Efficient, Magnetically Retrievable and Recyclable Oxidant
Lee, Ross A.,Donald, Dennis S.
, p. 3857 - 3860 (1997)
MagtrieveTM is a mild and selective oxidant for a variety of alcohols and, in addition to being magnetically retrievable, is superior to activated MnO2 in most cases - particularly for less active alcohols such as simple alkanes. - Key Words: chromium dioxide, manganese dioxide, oxidation, alcohols, aldehydes, ketones.
Isomerization of allylic alcohols to carbonyl compounds by aqueous-biphase rhodium catalysis
Bianchini,Meli,Oberhauser
, p. 11 - 12 (2001)
Isomerization of allylic and homoallylic alcohols is catalyzed by the zwitterionic Rh(I) complex (sulphos)Rh(cod) in water-n-octane to give the corresponding aldehyde or ketone in high yields and chemoselectivity. A π-allyl metal hydride mechanism is proposed on the basis of various independent experiments in both homogeneous and biphasic systems [sulphos = -O3S(C6H4)CH2C(CH2 PPh2)3].
Pd-Catalyzed Dehydrogenative Oxidation of Alcohols to Functionalized Molecules
Mori, Takamichi,Ishii, Chihiro,Kimura, Masanari
, p. 1709 - 1717 (2019)
A dehydrogenative oxidation reaction of primary alcohols to aldehydes catalyzed by a simple Pd/Xantphos catalytic system was developed under an argon or nitrogen atmosphere without oxidizing agents or hydrogen acceptors. The reaction product could be easily changed: under aerobic conditions, esters were obtained in aprotic solvents, whereas the corresponding carboxylic acids were produced in aqueous media. These oxidizing processes were applicable to the efficient synthesis of useful nitrogen-containing heterocyclic compounds such as indole, quinazoline, and benzimidazole via intramolecular versions of this reaction from amino alcohols.
Steinmetz et al.
, p. 1540 (1979)
Pd-Catalyzed Redox Divergent Coupling of Ketones with Terpenols
Zhao, Chao-Yang,Ji, Ding-Wei,Zheng, Hao,He, Gu-Cheng,Liu, Heng,Hu, Yan-Cheng,Chen, Qing-An
, p. 6825 - 6834 (2021)
Redox diversity is a common and important feature of nature. Herein, a Pd-catalyzed redox divergent coupling of ketones with terpenols has been developed to access α-substituted ketones with varying degrees of unsaturation. The control of oxidation states of the product is facilitated by employing different additives. With the aid of BnOH as an external hydrogen source, a reductive coupling pathway is thermodynamically favored. The use of LiBr as the additive will reduce the reactivity of Pd-H to divert the selectivity toward α,β-unsatuated ketones. By switching the solvent from toluene to chlorobenzene, the active species Pd-H will be fully quenched to enable oxidative coupling. Gram-scale reaction with lower catalyst loading (0.5 mol %) was also accomplished to highlight the practicability of this protocol. Furthermore, detailed experimental studies were carried out to elucidate the reaction mechanism and the factors enabling manipulation of the redox selectivity. This redox divergent coupling protocol provides an important complement for known precedents on Tsuji-Trost allylation of ketones.
Adames,G. et al.
, p. 491 - 492 (1972)
Palladium nanoparticles confined in the nanocages of SBA-16: Enhanced recyclability for the aerobic oxidation of alcohols in water
Ma, Zhancheng,Yang, Hengquan,Qin, Yong,Hao, Yajuan,Li, Guang
, p. 78 - 85 (2010)
Via modification of mesoporous cage-like material SBA-16 followed by adsorption of Pd(OAc)2 and reduction with NaBH4, Pd nanoparticles with a uniform size distribution were successfully confined in the nanocages of SBA-16, leading to a new solid catalyst for the aerobic oxidation of alcohols. The solid catalyst was characterized with N2 sorption, XRD, TEM, FT-IR and XPS. Such a catalyst showed a high activity for the oxidation of benzylic alcohols, 1-phenylethanol and allylic alcohols without the presence of bases under air or O2 atmosphere in water even at room temperature. The selectivities for the corresponding aldehydes and ketones were more than 99% in all the cases investigated. The developed catalyst could be facilely recovered and reused twelve times without significant decreases in activity and selectivity. Its recyclability was much better than that of the catalyst derived from amorphous silica under the same conditions.
Rhodium(I)-Catalyzed Intermolecular Aza-[4+3] Cycloaddition of Vinyl Aziridines and Dienes: Atom-Economical Synthesis of Enantiomerically Enriched Functionalized Azepines
Zhu, Chao-Ze,Feng, Jian-Jun,Zhang, Junliang
, p. 1351 - 1355 (2017)
A new synthetic application of vinyl aziridines as N-containing three-atom components in a rhodium-catalyzed [4+3] cycloaddition reaction is described. The reaction proceeds well with various silyl dienol ethers and vinyl aziridines, and enables the efficient synthesis of highly functionalized azepines in an enantioselective manner with net inversion of absolute configuration. The salient features of the transformation include the use of readily available substrates, high selectivity, and mild reaction conditions, as well as the versatile functionalization of the products.
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Riley,Silverstein
, p. 1957 (1974)
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Building MOF bottles (MIL-101 family as heterogeneous single-site catalysts) around Fe3O4 ships: A highly efficient and magnetically separable catalyst for oxidation of alcohols
Naghdi, Zahra,Farzaeli, Razieh,Aliyan, Hamid
, p. 1343 - 1350 (2015)
Fe3O4 supported on chromium-based metal-organic framework (MOF), MIL-101(Cr), has emerged as highly efficient and heterogeneous catalyst for selective oxidation of alcohols because of its high specific surface area, tuneable pore size, and unique structure. MIL-101 and its Fe3O4 composite (Fe3O4@MIL-101) was prepared via the impregnation of the Fe3O4 in MIL-101. The surface properties of the functionalized catalyst were analyzed by a series of characterization techniques like FTIR, XRD, N2 adsorption-desorption, and TEM. XRD and adsorption-desorption analysis show that the mesostructure of MIL-101 remains intact after Fe3O4 modifications, while spectral technique show the successful immobilizing of the neat Fe3O4 inside the MIL-101 support. Fe3O4@MIL-101 can be reused several times although they get less active.
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Mc Intosh,De Mayo
, p. 32 (1969)
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Controlling the selectivity of the manganese/bicarbonate/hydrogen peroxide catalytic system by a biphasic pyrrolidinium ionic liquid/n-heptane medium
Wong, Wing-Leung,Ho, Kam-Piu,Lee, Lawrence Yoon Suk,So, Ming-Him,Chan, Tak Hang,Wong, Kwok-Yin
, p. 244 - 249 (2013)
The Mn2+/HCO3-/H2O2 catalytic system exhibits excellent aldehyde selectivity in the oxidation of various benzylic and allyic alcohols under mild conditions and short reaction time when the reactions are carried out in a biphasic dicationic pyrrolidinium ionic liquid/n-heptane medium. The dicationic pyrrolidinium ionic liquid shows differential solubility towards alcohols and their aldehydes whereas the immiscible n-heptane instantaneously extracted and separated aldehydes from the reaction phase. This design of biphasic ionic liquid/n-heptane catalytic system prevents the over-oxidation of aldehydes to carboxylic acids effectively. Separation and recycling can also be easily done by decantation of the n-heptane layer after reaction. With the biphasic system, high conversion of benzyl alcohol to benzaldehyde was achieved with very low loadings of H 2O2 and Mn(OAc)2 catalyst at room temperature and within short reaction time. Throughout 10 reaction cycles, a total turnover number (TON) of 37,600 was achieved and excellent catalytic reactivity and selectivity were maintained with an average yield of 94%.
Structure, texture, acidity and catalytic performance of AlPO4-caesium oxide catalysts in 2-methyl-3-butyn-2-ol conversion
Bautista, Felipa M.,Campelo, Juan M.,Garcia, Angel,Leon, Raquel M.,Luna, Diego,Marinas, Jose M.,Romero, Antonio A.,Navio, Jose A.,Macias, Manuel
, p. 827 - 835 (1999)
A series of aluminium orthophosphate-caesium oxide systems with various caesium oxide loadings (5-30 wt%) were prepared by impregnation of ALPO4 with a methanolic solution of caesium acetate and characterized by TG/DTA, XRD, DRIFT, Raman, SEM-EDX, XPS, 27Al and 31P MAS NMR and nitrogen adsorption. Aluminium orthophosphate remained amorphous with caesium oxide incorporation when calcined at 873 K for 3 h. After thermal treatment at 1423 K it crystallized in the tridymite form except for materials containing 30 wt% caesium oxide. DRIFT spectroscopy showed that the P-OH stretching vibration at 3670 cm-1 decreased in intensity with caesium oxide loading. Materials at 20-30 wt% caesium oxide did not exhibit any hydroxyl bands. Besides, Al and P atoms remained in tetrahedral coordination as in unmodified aluminium orthophosphate. Moreover, the incorporation of caesium oxide leads, simultaneously, to a progressive decrease in surface area and pore volume (larger at 30 wt% caesium oxide) as well as to an increase in the most frequently occurring pore radius. On the other hand, caesium oxide reduced both the number and strength of acid sites as the caesium content increased. Consequently, 2-methylbut-3-yn-2-ol (MBOH) underwent almost exclusively dehydration to 3-methyl-3-buten-1-yne (acid activity) on pure AlPO4, whereas its modification with increasing amounts of caesium oxide developed AlPO4- based materials with increased basic properties and hence high selectivities (99 mol%) to the base-catalysed cleavage of MBOH yielding acetone and acetylene.
Oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds with aqueous hydrogen peroxide under organic solvent-free conditions
Kon, Yoshihiro,Usui, Yoko,Sato, Kazuhiko
, p. 4399 - 4400 (2007)
Allylic alcohols are chemoselectively oxidized to α,β- unsaturated carbonyl compounds in high yield with aqueous H2O 2 in the presence of Pt black catalyst under organic solvent-free conditions. The catalyst is easily recyclable and effective for at least 7 cycles. The Royal Society of Chemistry.
In situ synthesis of hierarchical In2S3-graphene nanocomposite photocatalyst for selective oxidation
Li, Xiuzhen,Weng, Bo,Zhang, Nan,Xu, Yi-Jun
, p. 64484 - 64493 (2014)
We report a simple, in situ hydrothermal way to fabricate In2S3-graphene (GR) nanocomposites in which hierarchical In2S3 "petals" spread over the surface of GR sheets in virtue of the "structure directing" role of graphene oxide (GO) as the precursor of GR in a solution phase. With the addition of an appropriate amount of GO, the hierarchical petal-like In2S3 structures have been successfully grown on the two-dimensional (2D) GR "mat". The as-synthesized In2S3-GR nanocomposites featuring good interfacial contact exhibit much higher photocatalytic activity toward selective oxidation of alcohols under visible light irradiation than blank In2S3. A series of characterization results disclose that the significantly enhanced photocatalytic performance of In2S3-GR nanocomposites can be ascribed to the integrative effect of the increased separation and transfer efficiency of photogenerated electron-hole pairs and the larger surface area. This work highlights the wide scope of fabricating GR-based semiconductor nanocomposites with specific architectural morphology by rationally utilizing the "structure directing" property of GO and extending their applications toward photocatalytic selective transformations. This journal is
Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral
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Page/Page column 8-10, (2021/04/14)
The present disclosure belongs to the technical field of catalysis, and particularly relates to a metal oxide coated ceramic corrugated plate catalyst, its preparation method and application thereof in preparation of key intermediates of citral. The catalyst consists of a ceramic corrugated plate carrier and a metal oxide active layer coated on a surface of the carrier, wherein the metal oxide active layer is a metal oxide formed by active ingredient titanium and at least four other metal elements selected from vanadium, chromium, manganese, iron, zirconium, niobium and molybdenum.
Method for synthesizing isovaleraldehyde
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Paragraph 0033; 0037; 0038; 0042-0043; 0048, (2020/12/05)
The invention provides a synthetic method of 3-methylcrotonaldehyde. The method comprises the following steps that epoxy isobutane is subjected to a hydroformylation reaction, hydroxy isovaleraldehydeis obtained, hydroxy isovaleraldehyde is subjected to an intramolecular dehydration reaction, and 3-methylcrotonaldehyde is obtained. The synthetic method of 3-methylcrotonaldehyde does not need harsh reaction conditions.
